Although ether‐based electrolytes have been extensively applied in anode evaluation of batteries, anodic instability arising from solvent oxidability is always a tremendous obstacle to matching with ...high‐voltage cathodes. Herein, by rational design for solvation configuration, the fully coordinated ether‐based electrolyte with strong resistance against oxidation is reported, which remains anodically stable with high‐voltage Na3V2(PO4)2O2F (NVPF) cathode under 4.5 V (versus Na+/Na) protected by an effective interphase. The assembled graphite//NVPF full cells display superior rate performance and unprecedented cycling stability. Beyond that, the constructed full cells coupling the high‐voltage NVPF cathode with hard carbon anode exhibit outstanding electrochemical performances in terms of high average output voltage up to 3.72 V, long‐term cycle life (such as 95 % capacity retention after 700 cycles) and high energy density (247 Wh kg−1). In short, the optimized ether‐based electrolyte enriches systematic options, the ability to maintain oxidative stability and compatibility with various anodes, exhibiting attractive prospects for application.
By rational design of the solvation configuration, a cation–solvent fully coordinated ether‐based electrolyte with strong oxidation resistance up to 4.5 V (versus Na+/Na) was developed and applied in graphite//NVPF and LHC//NVPF full cells which showed superior rate performance and unprecedented cycling stability.
The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence of specific interactions between active sites. Such interactions, referred to as long‐range ...interactions (LRIs), play an important role in determining the rate and selectivity of a reaction. The optimal combination of metal centres must be determined to achieve the targeted efficiency. To date, various types of DACs have been synthesised and applied in electrochemistry. However, LRIs have not been systematically summarised. Herein, the regulation, mechanism, and electrocatalytic applications of LRIs are comprehensively summarised and discussed. In addition to the basic information above, the challenges, opportunities, and future development of LRIs in DACs are proposed in order to present an overall view and reference for future research.
Diatomic catalysts have attracted much attention, especially in electrochemistry. However, there have been no comprehensive reviews on long‐range interactions (LRIs) between metallic centres. This Minireview introduces the key aspects of LRIs and highlights opportunities for regulating electrocatalytic mechanisms, thus presenting guidelines for the targeted usage of LRIs.
Summary
Microbial sulfate reduction is largely associated with anaerobic methane oxidation and alkane degradation in sulfate–methane transition zone (SMTZ) of deep‐sea cold seeps. How the sulfur ...cycling is mediated by microbes near SMTZ has not been fully understood. In this study, we detected a shallow SMTZ in three of eight sediment cores sampled from two cold seep areas in the South China Sea. One hundred ten genomes representing sulfur‐oxidizing bacteria (SOB) and sulfur‐reducing bacteria (SRB) strains were identified from three SMTZ‐bearing cores. In the layers above SMTZ, SOB were mostly constituted by Campylobacterota, Gammaproteobacteria and Alphaproteobacteria that probably depended on nitrogen oxides and/or oxygen for oxidation of sulfide and thiosulfate in near‐surface sediment layers. In the layers below the SMTZ, the deltaproteobacterial SRB genomes and metatranscriptomes revealed CO2 fixation by Wood–Ljungdahl pathway, sulfate reduction and nitrogen fixation for syntrophic or fermentative lifestyle. A total of 68% of the metagenome assembled genomes were not adjacent to known species in a phylogenomic tree, indicating a high diversity of bacteria involved in sulfur cycling. With the large number of genomes for SOB and SRB, our study uncovers the microbial populations that potentially mediate sulfur metabolism and associated carbon and nitrogen cycles, which sheds light on complex biogeochemical processes in deep‐sea environments.
It is still of great difficulty to develop the non‐platinum catalyst with high catalytic efficiency towards hydrogen evolution reaction via the strategies till now. Therefore, it is necessary to ...develop the new methods of catalyst designing. Here, we put forward the catalyst designed by the electronic metal–support interaction (EMSI), which is demonstrated to be a reliable strategy to find out the high‐efficiency catalyst. We carried out the density functional theory calculation first to design the proper EMSI of the catalyst. We applied the model of M1‐M2‐X (X=C, N, O) during the calculation. Among the catalysts we chose, the EMSI of Rh1TiC, with the active sites of Rh1‐Ti2C2, is found to be the most proper one for HER. The electrochemical experiment further demonstrated the feasibility of the EMSI strategy. The single atomic site catalyst of Rh1‐TiC exhibits higher catalytic efficiency than that of state‐of‐art Pt/C. It achieves a small overpotential of 22 mV and 86 mV at the at the current density of 10 mA cm−2 and 100 mA cm−2 in acid media, with a Tafel slope of 25 mV dec−1 and a mass activity of 54403.9 mA cm−2 mgRh−1 (vs. 192.2 mA cm−2 mgPt−1 of Pt/C). Besides, it also shows appealing advantage in energy saving compared with Pt/C (≈20 % electricity consuming decrease at 2 kA m−2) Therefore, we believe that the strategy of regulating EMSI can act as a possible way for achieving the high catalytic efficiency on the next step of SACs.
The electronic metal–support interaction (EMSI) is closely related to the electronic structure of active sites, which determines the catalytic activity. We put forward a method of designing the EMSI of single‐atomic site catalysts (SACs) to achieve high efficiency. The SACs achieve a lower overpotential and higher mass activity than any other SACs towards hydrogen evolution reaction, demonstrating the benefits of this method.
Sordariomycetes is one of the largest classes of Ascomycota that comprises a highly diverse range of fungi mainly characterized by perithecial ascomata and inoperculate unitunicate asci. Freshwater ...Sordariomycetes play an important role in ecosystems and some of them have the potential to produce bioactive compounds. This study documents and reviews the freshwater Sordariomycetes, which is one of the largest and important groups of fungi in aquatic habitats. Based on evidence from DNA sequence data and morphology, we introduce a new order Distoseptisporales, two new families, viz. Ceratosphaeriaceae and Triadelphiaceae, three new genera, viz.
Aquafiliformis
,
Dematiosporium
and
Neospadicoides
, 47 new species, viz.
Acrodictys fluminicola
,
Aquafiliformis lignicola
,
Aquapteridospora fusiformis
,
Arthrinium aquaticum
,
Ascosacculus fusiformis
,
Atractospora aquatica
,
Barbatosphaeria lignicola
,
Ceratosphaeria aquatica
,
C. lignicola
,
Chaetosphaeria aquatica
,
Ch. catenulata
,
Ch. guttulata
,
Ch. submersa
,
Codinaea yunnanensis
,
Conioscypha aquatica
,
C. submersa
,
Cordana aquatica
,
C. lignicola
,
Cosmospora aquatica
,
Cylindrotrichum submersum
,
Dematiosporium aquaticum
,
Dictyochaeta cangshanensis
,
D. ellipsoidea
,
D. lignicola
,
D. submersa
,
Distoseptispora appendiculata
,
D. lignicola
,
D. neorostrata
,
D. obclavata
,
Hypoxylon lignicola
,
Lepteutypa aquatica
,
Myrmecridium aquaticum
,
Neospadicoides aquatica
,
N. lignicola
,
N. yunnanensis
,
Ophioceras submersum
,
Peroneutypa lignicola
,
Phaeoisaria filiformis
,
Pseudostanjehughesia lignicola
,
Rhodoveronaea aquatica
,
Seiridium aquaticum
,
Sporidesmiella aquatica
,
Sporidesmium lageniforme
,
S. lignicola
,
Tainosphaeria lunata
,
T. obclavata
,
Wongia aquatica
, two new combinations, viz.
Acrodictys aquatica
,
Cylindrotrichum aquaticum
, and 9 new records, viz.
Chaetomium globosum
,
Chaetosphaeria cubensis
,
Ch. myriocarpa
,
Cordana abramovii
,
Co. terrestris
,
Cuspidatispora xiphiago
,
Sporidesmiella hyalosperma
,
Stachybotrys chartarum
,
S. chlorohalonata
. A comprehensive classification of the freshwater Sordariomycetes is presented based on updated literature. Phylogenetic inferences based on DNA sequence analyses of a combined LSU, SSU, RPB2 and TEF1α dataset comprising species of freshwater Sordariomycetes are provided. Detailed information including their habitats distribution, diversity, holotype, specimens collected and classification are provided.
Accurately distinguishing between enantiomeric molecules is a fundamental challenge in the field of chemistry. However, there is still significant room for improvement in both the enantiomeric ...selectivity (KR(S)/KS(R)) and binding strength of most reported macrocyclic chiral receptors to meet the demands of practical application scenarios. Herein, we synthesized a water‐soluble conjugated tubular host—namely, corral4BINOL—using a chiral 1,1′‐bi‐2‐naphthol (BINOL) derivative as the repeating unit. The conjugated chiral backbone endows corral4BINOL with good fluorescent emission (QY=34 % ) and circularly polarized luminescence (|glum| up to 1.4×10−3) in water. Notably, corral4BINOL exhibits high recognition affinity up to 8.6×1010 M−1 towards achiral guests in water, and manifested excellent enantioselectivity up to 18.7 towards chiral substrates, both of which represent the highest values observed among chiral macrocycles in aqueous solution. The ultrastrong binding strength, outstanding enantioselectivity, and facile accessibility, together with the superior fluorescent and chiroptical properties, endow corral4BINOL with great potential for a wide range of applications.
A pair of water‐soluble enantiomeric macrocycles was prepared using a chiral 1,1′‐bi‐2‐naphthol derivative as the building unit. The conjugated backbone results in the macrocycles having attractive chiral emissive properties, exceptional recognition affinity (up to 1010 M−1) and excellent enantioselectivity (up to 18.7) in water.
Chlorine evolution reaction has been applied in the production since a century ago. After times of evolution, it has been widely realized by the electrocatalytic process on anode nowadays. However, ...the anode applied in production contains a large amount of precious metal, increasing the cost. It is thus an opportunity to apply sub‐nano catalysts in this field. By regulating the tip effect (TE) of the catalyst, it was discovered that the oxidized sub‐nano iridium clusters supported by titanium carbide exhibit much higher efficiency than the single‐atom one, which demonstrates the significance of modifying the electronic interaction. Moreover, it exhibits a ≈20 % decrease of the electricity, ≈98 % selectivity towards chlorine evolution reaction, and high durability of over 350 h. Therefore, this cluster catalyst performs great potential in applying in the practical production and the comprehension of the tip effect on different types of catalysts is also pushed to a higher level.
The tip effect (TE) has not been mentioned enough in catalysts designing, having a large space to explore. Based on the model of oxidized sub‐nano clusters, the TE was regulated and found to be efficient in designing catalysts, making TiC perform a high activity during the chlor‐alkali industry. This cluster system exhibits great potential in applying in the practical production and the comprehension of the TE is also pushed to a higher level.
The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity ...storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center.
A catalyst with N‐heterocyclic carbene‐ligated Cu SAS as the active site, accompanied by many micro‐nano reactors, synergistically promotes the electrochemical synthesis of methane.
Summary
The low temperature and elevated hydrostatic pressure in hadal trenches at water depths below 6000 m render sample collection difficult. Here, in situ hadal water microbial samples were ...collected from the Mariana Trench and analysed. The hadal microbial communities at different depths were revealed to be consistent and were dominated by heterotrophic Marinimicrobia. Thirty high‐quality metagenome‐assembled genomes (MAGs) were retrieved to represent the major hadal microbes affiliated with 12 prokaryotic phyla. Most of the MAGs were newly reported and probably derived from novel hadal inhabitants as exemplified by a potentially new candidate archaeal phylum in the DPANN superphylum. Metabolic reconstruction indicated that a great number of the MAGs participated in nitrogen and sulfur cycling, in which the nitrification process was driven sequentially by Thaumarchaeota and Nitrospirae and sulfur oxidization by Rhodospirillales in the Alphaproteobacteria class. Moreover, several groups of hadal microbes were revealed to be potential carbon monoxide oxidizers. Metatranscriptomic result highlighted the contribution of Chloroflexi in degrading recalcitrant dissolved organic matter and Marinimicrobia in extracellular protein decomposition. The present work provides an in‐depth view on the hadal microbial communities regarding their endemism and element cycles.
Materials for Immunotherapy Shields, C. Wyatt; Wang, Lily Li‐Wen; Evans, Michael A. ...
Advanced materials (Weinheim),
04/2020, Volume:
32, Issue:
13
Journal Article
Peer reviewed
Breakthroughs in materials engineering have accelerated the progress of immunotherapy in preclinical studies. The interplay of chemistry and materials has resulted in improved loading, targeting, and ...release of immunomodulatory agents. An overview of the materials that are used to enable or improve the success of immunotherapies in preclinical studies is presented, from immunosuppressive to proinflammatory strategies, with particular emphasis on technologies poised for clinical translation. The materials are organized based on their characteristic length scale, whereby the enabling feature of each technology is organized by the structure of that material. For example, the mechanisms by which i) nanoscale materials can improve targeting and infiltration of immunomodulatory payloads into tissues and cells, ii) microscale materials can facilitate cell‐mediated transport and serve as artificial antigen‐presenting cells, and iii) macroscale materials can form the basis of artificial microenvironments to promote cell infiltration and reprogramming are discussed. As a step toward establishing a set of design rules for future immunotherapies, materials that intrinsically activate or suppress the immune system are reviewed. Finally, a brief outlook on the trajectory of these systems and how they may be improved to address unsolved challenges in cancer, infectious diseases, and autoimmunity is presented.
Immunotherapy has established a new paradigm for the management and treatment of diseases, leading to numerous clinical breakthroughs. The means by which materials have helped overcome critical barriers associated with emerging immunotherapies are reviewed, and new opportunities for their continued advancement are discussed.
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